Waterinsoluble azodyestuffs



hydrogen or an alkoxy group, or ethoxy group.

substratum, especially Patented Feb. 26, 1935 1,992,461 WATERINSOLUBLE AZODYESTUFF --Max Baltes and Kurt Briesewitz, l everkusen- I. G.-Wr k, and Arthur Zitscher, Offenbachv' on-the-Main, Germany, assignors to. General poi'atibn of Delaware Aniline Works, Inc., New York, N.

Y., a a cor- :NoDrawing. Application ApriLZ'l, 1934, serial N; 722,806; InGermany May 10, 1933 The present invention relates to new water: insoluble azodyestufis and to fibres dyed with the said dyestufis, more particularly it relates to dyestuffs of the probable general formula:

OH Hal wherein Hal stands for a halogen atom, such as a chlorine or bromine atom,

Hal

such as a methoxy Our new dyestufis are obtainable by diazotizing a 4.6-dihalogen-3 anisidine (Obi-1 :1) in the usual manner and coupling in substance or on a the vegetable fibre, with the anilide or a p-alkoxyanilide of 2 -hydroxynaphthalene-B-carboxylic acid.

Those dyestuffs prepared in substance are gen-- erally red powders and are valuable pigments, while those prepared on the fibre, especially the vegetable fibre, according to the usual processes of preparing ice colors generally yield red vivid shades of good fastness to light, chlorine and boiling. The dyeings are technically valuable because when produced by. a printing process as resists under dyeings of diazo salts of l-aminodiphenylamine or its substitution products they yield red shades of remarkable clarity and fastness to light.

The invention is illustrated by thefollowing examples, without being limited thereto:

Example '1 :-'-50'gram's-' of cotton yarn are impregnated for about half an hour in a solution prepared by dissolving 4.5 grams of 2.3-hydroxynaphthoic acid-p-anisidide in some water with the addition of 9 cos. of Turkey red oil of 50% strength, 9 cos. of aqueous caustic soda solution of 34 B and filling up with water to one litre. The cotton is squeezed and without rinsing in troduced for about minutes into a diazo solution prepared in the following manner:

1.92 grams of 4.6-dichloro-3-anisidine, having a melting point of 52 C., are diazotized, while cooling with ice, with 3.2 cos. of hydrochloric acid of 22 B and 0.72 grams of sodium nitrite. When the diazotization is complete,'excess mineral acid is neutralized by adding 2 grams of sodium acetate, then 20 grams of common salt are added, and the solution is filled up with water to one litre. A clear red of very good fastness to and stands for (or: iii-0:55)

neat stilts attaifi a; to the following formula:

OCH

-co-'-Nri oofis Eazample 2 .'50 grams of 'cottoif tis sue' pregnated for about half an hour in o'iie" litre,of

an impregnating bath, "prepared in th ,us ual. manner from 15 grams of 2.3-hydroxynaphthoic acid anilide. The cotton is rinsed, dried and printed with aprinting color prepared in the following manner:

13 grams of 4.6-di'chloro- 3 anisidine (OCI-Is: l) are dissolved with 22grarn's ofghydrochloric acid of 22 Bean'd 2 31 ccs. of water and dia'zotized, while cooling, with 22"gr'ams, ofso'dium nitrite and mixed with 500 v starch tra'gacanth thickener, acid is neutrali zed by adding 12 grams oi sodiu acetate, andthe whole is of aluminitun sulfate 1: 1.

one litre of an aqueous solutioncontai grams of diazotized I diphenylamine. After exposing for a short time to the air, the print is introduced into a bath containing in one litre5 cos. of hydrochloric acid of 22 B, rinsed at 70 C.',--soaped, again-rinsed and dried. A clear red is obtained beside aiull, red blue. The red dyestufi corresponds to the following formulas pared in the usual manner from 13 grams of 2.3-

hydroxynaphthoic acid anilide, 36 grams of The ayetis td e'i'pona rams f. ng tral A e fi i i ia dried and developed "on a twofrolls foular'd'v with 4-amino-4' -met aqueous caustic soda solution of 34 B, 24 grams of Turkey red oil and 1500 cos. of water. The cotton is then introduced for about 20 minutes into a diazo solution prepared in the following.

manner: I a

12 grams of 4-chloro-6-bromo-3-anisidine (OCH-13:1) of the melting point 51-52 C. are

N=N Br OO-NH By substituting the 2.3-hydroxynaphthoic acid anilide by an equivalent quantity of 2.3-hydroxynaphthoic acid-p-phenetidide, there are obtained similar shades. f

Example 4:-l9.2 grams of 4.6-dichloro-3-anisidine are diazotized in the usual manner with hydrochloric acid and sodium nitrite. The diazo solution is coupled with a solution prepared in the usual manner from 29,3 grams of 2.3-hydroxynaphthoic acid-p-anisidide in dilute aqueous caustic soda and Turkey red oil and containing sodium acetate in a quantity for binding the excess mineral acid. stuif separating is filtered and well After drying, it is obtained in form of a red powder which is soluble in concentrated sulfuric acid with a violet coloration.

The dyewashed.

. We claim: 1. Waterinsoluble azodyestuffs of the general formula:

V OCH: ragga OH lial wherein Hal stands for a halogen atom and :0 stands for hydrogen or an alkoxy group, being Hal -o O-NHOz wherein 'Hal stands for a chlorine or bromine atom and a: stands for hydrogen, a methoxy or ethoxy group, being generally red powders, and yielding, when produced on the fibre, generally red shades of good fastness to light, chlorine and boiling.

3. The Waterinsoluble azodyestuif of the following formula:

OOH;

4. The Waterinsoluble azodyestuff of the following formula:

O CH:

being a red powder, and yielding, when produced on the'fibre, red shades of good fastness to light, chlorine and boiling.

6. Fibres dyed with a dyestuff as claimed in claim 1.

7. Fibres dyed with a dyestufi as claimed in claim 2.

8. Fibres dyed with the dyestufi as claimed in claim 3.

9. Fibres claim 4.

10. Fibres in claim 5.

dyed with the dyestuff as claimed MAX BALTES. KURT .BRIESEWI'IZ. ARTHUR ZITSCHER dyed with the dyestufi as claimed in 

